Composite structure



ec. 22, 1942. F W, DUGGAN ET AL 2,306,046

COMPOS ITE STRUCTURE Filed May l2, 1939 V//VYL @E S /N C OMPOS TIO/V W/TH WAX WAX sou/ENT APPL/0 46 HEA T50 "wmf/NG @ULL u g coMpos/T/o/v W/THOUT WAX HEAT@ OLS /lj WAX ATTORNEY atented @ed 22, ist@ ascesi@ erario @l -f-f Application May 12, i939, Serial No. 273,202

li Ciaims. (Cl. il7-Ji2) invention is directed to the production oi tinuously forming a lm of vinyl resin composi- -osite structures of the class in which at least tion by the aid of heat and pressure, maintaining uriace cia porous and fibrous sheet material, the formed film at an elevated temperature, and cloth and paper, is provided with an adcontinuously pressing this heated lm against a coating of a vinyl resin composition adapt- F oase sheet material with which it is to be como render the resulting composite structure bined to form the desired composite. The comiznpervious to the transmission of water posite material is then further treated to achieve liquids and vapors. the desired degree of imperviousness to water and posits structures oi this class are lmown, the like, all as more fully hereinafter described. ous methods for making them have been 10 To facilitate an understanding of the invention, For example, it has been suggested reference may pe had to the accompanying draw-- protective coating containing a rvinyi ing, wherein:y y'oe applied to sheet materialsinthe form Fig. 1 diagrammatically illustrates a method rnish or iacquer. This method is `not and apparatus for calenderlng onto one side ci a satisfactory when applied to brous mai5 hase, a coating of vinyl resin composition conuch as cloth or paper, for the reason that taining wax, and applying a wax solvent; ay fibers which escape complete coatu Fig. 2 diagrammatically illustrates a method which, acting as wicks, tend to defeat and apparatus for calendering onto both sides of of coating as :far as imnervious- `nase, a coating of vinyl resin composition is concemed. .also this method ci 20 thereafter applying Wax and further processiie o. which e. solution of the vinyl resin com the material; y n isrequired, necessitates handling the wet Fig. 3 shows a section through the.material reduci, prior to drying, and the loss processed as illustrated in Fig. Land riven ofi during drying, or the cost oi Fig. 4 shows a section through the material las solvents. processed as illustrated in Fig. 2. proposed methods for making the comin practice this process is most conveniently terials o?? the class with which this incarried out by calendering the vinyl resin comconcerned have, included hot-pressing position ii against one or both surfaces of a 'oase i nlm of the winyl resin compositionin n sheet i2, such as paper or fabric, under such with the material to be coated, and the "n conditions of temperature and pressure as to re procedure oi applying powdered vinyl suit in iirm union of an unbroken film of the vinyl imposition over the material on which resin composition of the thickness desired with desired. and pressing under the iniiuu the lease sheet to form a composite material. "neat to flow the vinyl resin and form a Thereafter a vinyl resin-bearing surface oi this Both of these methods have the dis 5 material is given a treatment whereby a tightly se of `being discontinuous since a press is adherent, very thin, wax-containing coating oi and, while the nist-named procedure maximum imperviousness to liquids and vapors, s made continuous by pressing the preparticularly water, is produced on it. This latter ed nlm and rthe material to be coated between treatment may, in general, assume one of three rollers, the process still possesses the dism fonns. First, the Wax may be heated to a molten or" requiring the additional step oi or near-molten state or it may be dispersed or the initially. dissolved in liquids which do not attack the vinyl invention largely obviates the disadvanresin surface of the material, and in this form previously known processes for making mechanically applied, for instance by wicks i3, materials which comprise a surface as a thin laver it which can oe polished or or coatings or vinyl resin composition. burnished, as by rollers i5, to convert it into tile lpal object of the invention is to provide desired continuous, thin and adherent form which ved, economical and eicient process we have found capable of affording maximum pro e of continuous operation for produca-f,l tection. Second, the wax may be applied as an materials having at least one surface o emulsion in an aqueous menstruum employing as an impervions vinyl resin composition. the emulsiiying agent a material which isili not itlon also includes the new composite allow the wax iilm deposited from the emulsion to be redispersed on contact with water. Third, i i recess by means oi7 which the objects of the Wax may be employed as a component of the this on are attainedbroadly comprises con' vinyl resin composition initially joined to the base sheet and. by the action of a liquid which is a solvent for the wax, and a penetrant, but not a solvent for the vinyl resin, subsequently applied, as by sprayer I6, to this composition, it may be broughtl to the surface and formed into a continuour film.

The vinyl resins used in the compositions of this invention may be those produced by the polymerization of vinyl esters including vinyl halides and vinyl esters of aliphatic acids, and the invention is primarily concerned with compc:.-ons containing vinyl resins such as may be fai-ned by the conjoint polymerization of Vinyl haiides with vinyl esters of aliphatic acids. In resins of this class, in which the vinyl halide predominates and preferably constitutes from 70% to 95% by weight of the polymer, are found the most desirable properties for use in the practice of this invention. Specifically, resins which may be made by the conjoint polymerization of vinyl chloride with vinyl acetate and which contain from 80% to 90% by weight of the chloride are most desirable. Other components of the vinyl resin composition may include stabilizers, such as the metal soaps of which calcium stearate and lead stearate are typical, and lubricating materials, such as mineral oils or paraffin and carnauba wax. The composition may be colored by means of pigments, lakes or dyes if desired. It may be rendered flexible and soft in any desired degree by including plasticizers for the vinyl resin. Examples of suitable plasticizers are such high boiling esters as dibutyl phthalate, dibeta butoxyethyl) phthalate, dichlorethyl phthalate, tricresyl phosphate, dibutyl tartrate and related substances.

The final treatment of the vinyl resin surface of the composite material to attain the degree of imnermeability to water and the like which is achieved by this invention involves the use of a high melting (that is, above about 65 C.) parafdn or similar high melting Wax of hydrocarbon nature, such as ceresin or beeswax, capable of f.:- ng in crystalline or pseudo-crystalline form. caer melting point waxes can be used with somewhat less desirable results.

The ingredients referred to may be present in the nyl resin composition used in various pro poinons chosen according to the properties desired in the material produced. In general, for compositions of adequate flexibility and softness vinyl resin may be combined with from about to about 30% by weight of a plasticizer and from about 1% to 3% of stabilizer and lubricant material combined. If the wax is incorporated in the vinyl resin composition, from 0.5% to about 5.0% is usually sufficient.

The union of a surface iilm of the vinyl resin composition to a base sheet, such as paper, can be effected by the use of a multi-roll calendering machine. 1For example, the vinyl resin composition in which the ingredients have been previously combined by any suitable means can be caused to pass between the first and second rolls, I7 and i5, respectively, of a three roll machine to form a film of somewhat greater thickness than that which actually is to be secured to the base sheet. This hlm passes around the second roll to enter the opening between that roll and the third roll f5. The sheet i2 of material to be coated is passed into the opening between the second and third rolls together with the vinyl resin illm so that it is pressed in contact with the film. By adjustment of the openings between the rolls, the thickness of the film of resin composition and the pressure with which it is forced against the base sheet can be closely regulated. It is usually desirable to maintain such relative sizes of the openings between the rolls as to cause a reduction in the resin film thickness as it joins the base sheet material. compensation for any inequalities in the surface or thickness of the resin film or base sheets as the resin film approaches contact with the base sheet.

The calendering rolls may be heated by steam supplied to their interiors, or by other means as desired. The temperature required for the sev eral rollers involved in this operation will vary according to the thermoplasticity of the vinyl resin composition used, the thermal conductivity of the sheet material being coated, and the extent of penetration of the resin composition desired in the case of fibrous or porous sheet materials. In general, the initial forming of the resin film requires a temperature of about to about C. and this may be conveniently maintained by means of steam supplied to the calender rolls at gauge pressures of about 35 to about 60 pounds per square inch.

The application of the coating of vinyl resin composition to both sides of the base sheet material can be carried out in the same way. In case this is desired, it is only necessary that a four roll calendering machine be employed so that two preformed films can be made simultaneously between the first and second and the third and fourth rolls, while the sheet material to be coated enters the opening between the second and third rolls together with each of the two films so formed.

It is desirable, although not essential. that the base sheet material be preheated before coming in contact with the resin composition. This can be conveniently effected by passing the sheet material around a heated drum, an additional. calender roll, or merely around or somewhat more, of the circumference of the third roll of a three roll machine used to coat only one side of the material.

The treatment of the coated material to obtain the exceptionally high degree of imperviousness to moisture transmission made possible by this invention Will be discussed in each of its three embodiments in the examples to follow.

Example 1 'I'he first of these embodiments involves melting the wax, or dissolving the wax in a liquid which will not attack by dissolution or otherwise, the vinyl resin finish of the composite structure. and thereafter applying the liquid compositions thus formed to the vinyl resin surface. The application of the molten Wax is preferably carried out by spreading the liquid wax over the vinyl resin surface while' maintaining the composite structure at a temperature of about '75 C. to about 125 C. Means for thus spreading the liquid wax which have proved very effective include spraying, application by roller coating. and bringing the vinyl resin surface in contact with a wick of felt material thoroughly impregnated with the liquid composition. The applied wax coating is burnished by a rubbing treatment and the assembly permitted to cool. Rapid cooling may be carried out by passing the composite structure around a chilled roll 20 and results in enhanced brightness, lustre. and smoothness of the finished coating, caused. perhaps, by crystallization of the wax surface.

This accomplishes automatic When the wax is applied as a solution in a liquid inert toward the vinyl resin finish, applicationmay be by any convenient means, such as by spraying or by roller coating, and the composite structure being treated need not necessariiy be heated. Upon removal of the liquid by evaporation, the wax is deposited on the vinyl resin surface and the wax coating may be burnished and evenly distributed by rubbing.

in each case, a smooth and very adherent waxcoritaining coating is deposited and the resistance of the treated composite structure to the transmission of Water and other liquids and vapors was remarkably increased. For instance, a composition of the following components was prepared:

Parts resin 78.9 im. a-butoxy-ethyl) phthalate 18.0 Carnauba wax i3 Calcium stearato 0.8

vinyl resin was made by the conjoint polymerization oi vinyl chloride with vinyl acetate and contained about 87% vinyl chloride in the polymer.

t s composition was calendered on medium solicite paper and a vinyl resin coating apm .iximately 0.002 inch in thickness was formed, rate or" moisture transmission through the coated was found to be 9.15 mgm./hr./so.

were not observably different from resin coated paper prior to treatment surface of the treated paper was bright 'nparatively hard. .le use the high melting parafdn wax in. embodi'i-ent oi the invention is of impor The lower melting waxes, such as those ""o. melt around 52 C., are less satisfactory lince their application results in a soft, id greasy nish on the coated paper.

Example 2 The second embodiment of the process of treattbe vinyl resin surface ci' the composite re involves applying the Wax as an emuloi in Water employing as the emulsifying agent material which will not permit the Wax to be ed on contact with Water, The emul- 'oe applied to the vinyl resin surface .y convenient manner, such as by roller in which a doctor blade is used to con- ',fie distribution oi the applied emulsion or rai/ing. Emulsifying agents which may be clude fatty acid soaps oi morpholine, such orpheline cleats and morpholine stearato tty acid soaps of ammonia, such as amn n oleate.

manner of preparation of the emulsions will oe illustrated by sei/eral specic illustrations. The proportions subsequently mentioned are by weight.

n laurate. ami'nonium stearato, and am- One hundred and seventy-six (176) parts of a parafiin wax melting at about C. were melted with 18 parts of stearic acid by heating to about C. This melted mixture was added with vio lent agitation to a boiling solution. of 4.3 parts or? morpholine in 600 parts of water. The resulting emulsion was of the oil-in-Water type. It was permitted to cool under moderate stirring to room temperature and it was observed that such an emulsion. was very stable.

Another emulsion was prepared in a. similar manner by heating a mixture of 88 parts of the paraflin Wax, 88 parts of toluene, and i8 parts oi oleic acid and dispersing the molten mixture in a. boiling solution of 4.3 parts of morpholine in. 600 parts of water. On cooling, a stable emulsion of the oil-in-water type was again obtained.

These emulsions were applied by spraying to the vinyl resin surface of a paper coated with vinyl resin. The manner of preparation of the coated paper was similar to that described in Example l. During the spraying, the emulsions were maintained at room temperatures, Whereas the temperature of the vinyl resin surface was permitted to vary between 20 C. and 136 C. It was observed that more uniform distribution oi the emulsion was obtained when the vinyl resin. surface was maintained at the higher tempera tures. Upon evaporation of the water and any other volatile constituents of the applied emulsion, a. uniform, hard, adherent, and very thin wax-containing coating was formed on the vinyl resin surface. This coating showed no tendency to redisperse on Contact with Water despite the residual amount of emulsifying agent present. The resistance of the vinyl resin coated paper to moisture transmission was markedly increased by the presence of the Wax-containing coating. many cases this increase was as much as si-'l fold and in no case was it less than four .old,

ln this embodiment of the invention, a lower melting Wax may be employed with results al most as satisfactory as those which may be ob tained by the use of the higher melting waxes.

Example 3 The third embodiment of the method of treatw ing the vinyl resin surface ot the composite structure involves originally incorporating the hydro carbon wax in the vinyl 'resin composition and subsequently applying to the vinyl resin surface n liquid which is a solvent for the wax and n penetrant or swelling agent, but not a solvent. for the vinyl resin. The effect of this treatment is greatly to increase the resistance of the composite structure to moisture transmission, possibly induced by'a rearrangement of the vinyl resin coating under the iniiuence of the liquid so as to bring the wax constituent of the coating comN position to the surface. Suitable liquids for use in this treatment include aromatic hydrocarbons, such as benzene, toluene, and xylene and solventdiluent or solvent-non-solvent mixtures in which sufiicient diluent or non-solvent is present in the mixture so that the mixture. taken as a whole. does not dissolve the vinyl resin. Solvents for the' vinyl resin include acetone, methyl ethyl ketone. methyl isobutyl ketone, ethyl acetate, butyl acetate, and ethylene dichloride: diluentri include benzene, toluene, xylene, and tetrahydro naphtnalene: non-solvents include parafiin hydrocarbons, alcohols, aldehydes, and others.

Several modes of practicing this embodiment of the invention will now be given. A vinyl resin coating having the following composition was prepared:

sThe vinyl resin was substantially the same as that described in Example l.

This vinyl resin coating composition was cale; ered onto a suitable paper backing. The vinyl surface was treated with the appropriate liquid in several ways;` by roller coating, by bringthe vinyl resin surface in Contact with a wick ated with the liquid, and by spraying. ig was found most effective and it Was sirably carried out by applying a. very :r fray of the liquid to the vinyl resin surface.

"i Lis manner the wax was eiectively brought surface of the vinyl resin coating Without e ly softening the Vinyl resin coating.v After treatment the wetted composite films were :it 60 C., for instance by passing in contact a drying roll El, although other temperaare satisfactory. after applying a spray of toluene in this manner to the vinyl resin surface, it was found that the resista-nce of the composite film to moisture transmission was increased from two to four Itimes. It was further found that improvement in these results could be obtained by incorporatin the treating liquid a small amount (about 1% of the liquid) ofwax, or of a natural or artificial gum, such as a modied alkyd resin, or a mixture of wax and gum. Under these conditions, resistance ci the composite film to moisure transmission was increased about four to .,'.;v: times and the results were more easily regni-odi. ible. Treatment of the vinyl resin surface with a solvent for the vinyl resin, such as one or ethylene dichloride, did not affect the i ure resistant properties of the composite .Tvodications of the invention other than as described in the above examples will be apparent to those versed in the art to which the invention appcrtains and are included within the scope of the invention as defined in the appended claims.

We claim:

". il composite structure highly impervious to transmission of water vapor, comprising a f porous and brous material rrnly a substantially unbroken nlm of vinyl calendered thereon, said film being assisted ting the transmission of water vapor by the presence on the film of a continuous, adherent, and very thin coating essentially comor 'ng a hydrocarbon wax.

1. composite structure highly impervious to the 'transmission of water vapor, comprising a sheet of porous and brous material firmly bonded to a substantially unbroken film of vinyl calendered thereon, said lm being assisted .in r isting the transmission of water vapor by the presence on the film of a continuous, adherent, very thin coating essentially comprisii f hydrocarbon wax, said vinyl resin being iially identical with that resulting from l ,onoint polymerization of a vinyl halide u it'n vinyl ester oi a lower aliphatic acid.

3. fr composite structure highly impervious to the transmission of water vapor, comprising a sheet of porous and nbrous material firmly bonded to a substantially unbroken lm of vinyl resin calendered thereon, said lm being assisted in resisting the transmission of water vapor by the presence on the film of a continuous adherent, and very thin coating essentially comprising a high melting hydrocarbon wax, said vinyl resin being substantially identical with that resulting from the conjoint polymerization of vinyl chloride with vinyl acetate.

4. A composite structure highly impervious to the transmission of water vapor comprising a sheet of porous and brous. material firmly bonded to a substantially unbroken lllm of vinyl resin calendered thereon, said film being assisted in resisting the transmission of water vapor by the presence on the film of a continuous, adherent, and very thin coating essentially comprising a paraiin wax melting above about 65 C.

5. A composite structure highly impervious to the transmission of water vapor, comprising a sheet of porous and fibrous material firmly bonded to a substantially unbroken film of vinyl resin calendered thereon, said nlm being assisted in resisting the transmission of water vapor by the presence on the lm of a continuous, adherent, and very thin coating essentially cornprising a paraffin wax melting above about 65 C., said vinyl resin being substantially identical with that resulting from the conjoint polymerization of a vinyl halide with a vinyl ester of a lower aliphatic acid.

6. A composite structure highly impervious to the transmission of water vapor, comprising a sheet of porous and fibrous material firmly bonded to a substantially unbroken nlm of vinyl resin calendered thereon, said lm being assisted in resisting the transmission of water vapor by the presence on the film of a continuous, adherent, and very thin coating from approximately 0.00005 to approximately 0.0001 of an inch in thickness essentially comprising a parain wax melting above about 65 C., said vinyl resin being substantially identical with that resulting from the conjoint polymerization of vinyl chloride with vinyl acetate, said composite structure having a moisture transmission between approximately 0.01 and approximately 0.03 mgm. per hour per sq. cm. at approximately 30 C. under the condition of saturated water vapor on one side of the structure and dry atmosphere on the other side.

7. Process for making a composite structure highly impervious to the transmission of water vapor, which comprises firmly adhering a substantially unbroken film of vinyl resin composition on a sheet of porous and fibrous material by calendering, and thereafter forming on said film a continuous, adherent, and very thin coating of a hydrocarbon wax adapted to assist said vinyl resin lm in resisting the transmission of Water vapor.

8. Process for making a composite structure highly impervious to the transmission of water vapor, which comprises rmly adhering a substantially unbroken lm of vinyl resin composition on a sheet of porous and fibrous material by calendering, applying to the film thus deposited a molten composition comprising a hydrocarbon wax. and forming on said lm a continuous, adherent, and very thin coating of said wax adapted to assist said vinyl resin film in resisting the transmission of water vapor.

9. Process for making a composite structure highly impervious to the transmission of water fik vapor, which comprises firmly adhering a substantially unbroken nlm of vinyl resin composition on a sheetof porous and fibrous material by calendering, applying to the lm thus deposited a molten composition comprising a hydrocarbon Wax melting above about 65 C., and forming on said film and continuous, adherent, and very thin coating of said wax adapted to assist .said vinyl resin nlm in resisting the transmission of Water vapor, said vinyl resin being substantially identical with that resulting from the conjoint polymerization of vinyl chloride with vinyl acetate.

lo. Process for making a composite structure highly impervious to the transmission of water vapor, which comprises firmly adhering a substantially unbroken film of vinyl resin composition on a sheet of porous and fibrous material by calendering, applying to the film thus deposited a molten composition comprising a hydrccarbon wax melting above about 65 C., rapidly cooling the applied molten wax, and forming on said lm a continuous, adherent, very thin coating of said Wax adapted to assist said vinyl resin lm in resisting the transmission of Water vapor, said vinyl resin being substantially identical with that resulting from the conjoint polymerization of vinyl chloride with vinyl acetate.

il. Process for making a composite structure i highly impervious to the transmission of Water vapor, which comprises calendering a substantially unbroken film of vinyl resin composition on sheet of porous and fibrous material to give an adherent coating thereon and applying to the nlm thus deposited an emulsion comprisa hydrocarbon wax dispersed in water by of an emulsifying agent, said emulsifyi agent being selected from the group consistof morpholine and ammonium salts of fatty "ds, removing the volatile constituents from mulsion, and forming on said ilm a con- 'is, adherent, and very thin coating of said adapted to assist said vinyl resin film in thc transmission of water vapor Process for making a composite structure highly Lmpervicus to the transmission of water vapor, which comprises calendering a substantially unbroken fili-fn of Vinyl resin composition on a sheet of porous and fibrous material tc give an adherent coating thereon and applying to the film thus deposited an emulsion comprism ing a hydrocarbon wax melting above about 65 C. dispersed in water by the aid of an emulsifying agent, said emulsifying agent being selected from the group consisting of morpholine and ammonium salts of fatty acids, removing the volatile constituents from the emulsion, and forming on said film a continuous. adherent, and very thin coating of said wax adapted to assist said vinyl resin film in resisting the transmission of water vapor, said vinyl resin being substantially identical with that resulting from the conjoint polymerization of vinyl chloride with vinyl acetate.

13. Process for making a composite structure highly resistant to the transmission of water vapor, which comprises incorporating a hydro carbon wax in a vinyl resin composition, firmly adhering a nlm of said vinyl resin composition on a sheet of porous and fibrous material by calendering, and thereafter applying to said nlm a liquid, said liquid being a solvent for said Wax and a penetrant, but not a solvent, for said vinyl resin, and causing the Wax contained in said film to reform-itself mostly on the surface of said vinyl resin. film, said refoimed Wax surface being adapted to assist the vinyl lresin lm in resisting the transmission of Water vapor.

14. Process for making a composite structure highly resistant to the transmission of Water vapor, which comprises incorporating a hydrocarbon Wax melting above about 65 C. in a Vinyl resin composition, firmly adhering a lm of said vinyl resin composition on a sheet of porous and fibrous material by calendering, and thereafter applying a liquid aromatic hydrocarbon to said film, and causing the Wax contained in said film to reform itself mostly on the surface ci said vinyl resin film, said reformed wax surface being adapted to assist the vinyl resin lm in resisting the transmission of Water vapor, said vinyl resin being substantially identical with that resulting from the conjoint polymerization of vinyl chloride with vinyl acetate.

FRED W. DUGGAN. FRAZIER- GROFF. 

